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WO2025003654A1 - Module de réacteur - Google Patents

Module de réacteur Download PDF

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Publication number
WO2025003654A1
WO2025003654A1 PCT/GB2024/051627 GB2024051627W WO2025003654A1 WO 2025003654 A1 WO2025003654 A1 WO 2025003654A1 GB 2024051627 W GB2024051627 W GB 2024051627W WO 2025003654 A1 WO2025003654 A1 WO 2025003654A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat exchanger
process fluid
catalyst
inlet
module
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/GB2024/051627
Other languages
English (en)
Inventor
Peter Gray
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Catalsys Ltd
Original Assignee
Catalsys Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Catalsys Ltd filed Critical Catalsys Ltd
Publication of WO2025003654A1 publication Critical patent/WO2025003654A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0206—Non-hydrocarbon fuels, e.g. hydrogen, ammonia or carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0218—Details on the gaseous fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
    • F02M21/0227—Means to treat or clean gaseous fuels or fuel systems, e.g. removal of tar, cracking, reforming or enriching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls

Definitions

  • the present invention relates to a reactor module for carrying out an ammonia cracking reaction, to a catalyst cartridge for that module, and to a fuel system using such a reactor module.
  • Hydrogen fuel has been proposed as a clean energy solution that, if adopted, could reduce the CO2 emissions associated with the world’s energy production and consumption. Hydrogen is considered to be a ‘clean’ fuel as it can be created using zero carbon renewable power and consumed and produce water as the sole or major product under the correct conditions. Hydrogen can be stored in gaseous or liquid form and transported as a means of delivering energy to locations and end-users. The transportation of hydrogen presents various challenges. The cost of green hydrogen to the end-user in geographies where it is most in demand such as Europe, North America, and Asia is not economic which impedes the decarbonisation of major CO2 emitting industries such as transport and heating. Green hydrogen produced in the regions of demand is often made via the electrolysis of water using renewable electricity.
  • the Haber-Bosch process is a well-known equilibrium process that is most commonly used to produce ammonia for applications such as fertiliser through the reaction of hydrogen and nitrogen.
  • the reaction of hydrogen with nitrogen is a reversible reaction, with the forward reaction producing ammonia (the Haber-Bosch process).
  • the manipulation of reaction conditions allows for ammonia to be converted back into hydrogen and nitrogen (known as cracking) and these two reactions occur together to produce an equilibrium.
  • the reliance of world agriculture upon ammonia-based fertilisers has created an ammonia transportation infrastructure that is well-established.
  • Transportation of liquid ammonia has various advantages when compared to the transportation of liquid or gaseous hydrogen.
  • the boiling point of hydrogen is approximately -253°C whereas the boiling point of ammonia is approximately -33°C.
  • ammonia is significantly less energy intensive to liquify and store in liquid form. Ammonia is less flammable than hydrogen and so is considered safer to transport. The energy density of liquid ammonia is also significantly greater than that of liquid hydrogen. Both ammonia and hydrogen can be used as fuels.
  • the present invention provides an ammonia cracker reactor module comprising a heat exchanger, and a catalyst cartridge, wherein: the reactor module comprises a process fluid module inlet, a process fluid module outlet, a working fluid module inlet and a working fluid module outlet; the heat exchanger and catalyst cartridge are arranged such that a process fluid entering the reactor module through the process fluid module inlet passes through the catalyst cartridge and heat exchanger before passing to the process fluid module outlet; the catalyst cartridge comprises a catalyst material arranged to contact a process fluid passing therethrough to catalyse a reaction to convert ammonia in the process fluid into hydrogen; the heat exchanger is arranged such that a working fluid entering the reactor module through the working fluid module inlet passes through the heat exchanger before passing to the working fluid module outlet, the heat exchanger being arranged to transfer heat between a process fluid and a working fluid flowing therethrough; the catalyst cartridge is removably associated with a process fluid heat exchanger inlet and I or a process fluid heat exchanger outlet such that the catalyst cartridge can be separated from the heat exchanger
  • the catalyst cartridge can be created and tested separately from the heat exchanger meaning that any failure in integrating the catalyst in to the cartridge, for example by coating the catalyst onto relevant surfaces of the cartridge, requires only the replacement of the catalyst cartridge and not the entire heat exchanger which would be required if the catalyst was coated directly onto the internal surfaces of the heat exchanger.
  • the reactor module may comprise additional components, for example a housing within which at least some, or all, of the other components are located, additional catalyst cartridges or electrically heated catalysts.
  • the process fluid module inlet, process fluid module outlet, working fluid module inlet and working fluid module outlet may be provided as pipes, tubes, or other connectors which are accessible from outside the reaction module and to which other pipes, tubes, or connectors can be coupled.
  • a suitable connection is a flanged pipe end which can be bolted to another flanged pipe end, but other connection mechanisms are possible, including, for example, clamping or welding.
  • the heat exchanger may be any suitable form of heat exchanger capable of carrying out the required duty.
  • a welded plate heat exchanger having a shell side fluid and a plate side fluid has been found to be particularly suitable.
  • the heat exchanger has a process fluid heat exchanger inlet, a process fluid heat exchanger outlet, a working fluid heat exchanger inlet and a working fluid heat exchanger outlet. These inlets and outlets can be coupled to further process equipment, pipes, or other components.
  • the catalyst cartridge is removably associated with a process fluid heat exchanger inlet and I or a process fluid heat exchanger outlet such that the catalyst cartridge can be separated from the heat exchanger.
  • the catalyst cartridge may be removably associated with a process fluid heat exchanger inlet and / or a process fluid heat exchanger outlet by being immediately upstream ordownstream of the inlet or outlet with which it is associated.
  • the catalyst cartridge may be located within the heat exchanger, outside the heat exchanger or partially inside and outside the heat exchanger.
  • the catalyst cartridge may comprise a cartridge housing within which catalyst material and / or a support for a catalyst material may be housed. This may protect the catalyst material and / or provide flow channels to direct flow around, or through the catalyst material.
  • the cartridge housing may be fabricated from a metal.
  • the cartridge housing may extend along an axis and may comprise an axial opening.
  • the axial opening may be connected to one or more radial opening by one or more flow channels. A fluid passing along the one of more flow channels between the axial opening and the one or more radial openings may contact the catalyst material.
  • the housing may be configured for insertion into and / or movement within an inlet or outlet manifold of a heat exchanger.
  • the catalyst cartridge may be movable, for example by pushing, or pulling, by an actuator to different positions relative to the heat exchanger.
  • the position may be pre-set prior to use, or may be dynamically adjusted during use, of the reactor module.
  • the catalyst cartridge may be movable between a position in which it is fully within the heat exchanger to a position in which the catalyst cartridge is at least partially outside the heat exchanger. Positioning the catalyst cartridge at least partially outside the heat exchanger may provide, or increase the size of, a flow path for process fluid that bypasses the catalyst cartridge. Moving both catalyst cartridges to a position in which they are at least partially outside the heat exchanger may provide a flow path though the heat exchanger which bypasses any catalyst cartridges within the heat exchanger.
  • Moving a catalyst cartridge in this way can alter the properties of the reactor module for different operating modes, for example start-up or shutdown, for example by dynamically varying the hydrogen/ammonia ratio by increasing or decreasing the proportion of process fluid that passes through the catalyst cartridge, and / or increasing or decreasing the residence time of process fluid within a catalyst cartridge.
  • the catalyst material within the catalyst cartridge may include one or more metals which may include precious metals.
  • the catalyst material may include nickel, cobalt, iron, ruthenium, or any combination thereof.
  • the catalyst material may be supported in that the catalyst material may include, be supported upon, and/or dispersed throughout a support material.
  • Suitable support materials may include metals, ceramics, porous materials such as zeolites, carbon materials such as activated carbons, inorganic materials such as calcium imide, any other suitable support material, or any combination thereof.
  • the support material may include carbon.
  • the support material may include alumina.
  • the support material may include ceria.
  • the support material may include zirconia.
  • the support material may include yttria.
  • the support material may include a basic material.
  • the process of cracking ammonia into hydrogen and nitrogen is endothermic and cools the process fluid as cracking occurs. This cooling of the process fluid slows the cracking process and, as the process is an equilibrium reaction, the percentage of conversion from ammonia into hydrogen may be reduced. Heating the process fluid helps to maintain its temperature and so increases the percentage of conversion into hydrogen.
  • the present invention uses a working fluid passing through a heat exchanger to heat the process fluid to encourage the cracking reaction. This allows the process fluid to be heated by cooling a working fluid stream.
  • the working fluid stream may be a waste stream, such as an exhaust from an engine which may be fuelled by the hydrogen produced in the reaction module, or a stream from a different process.
  • the catalyst cartridge in the reactor module may be a first catalyst cartridge and the reactor module may comprise a second catalyst cartridge which may increase the conversion from ammonia into hydrogen.
  • the second catalyst cartridge may be in a parallel arrangement with the first catalyst cartridge, or the second catalyst cartridge may be located upstream, or downstream of the first catalyst cartridge along the process stream in a series arrangement.
  • the process stream may pass through at least some of the heat exchanger between passing through the catalyst cartridge and the second catalyst cartridge. This allows the process fluid to be heated between the catalyst cartridges.
  • the catalyst cartridge may be associated with a process fluid heat exchanger inlet and the second catalyst cartridge may be associated with a process fluid heat exchanger outlet. This may allow the process stream to pass through the catalyst cartridge associated with a process fluid heat exchanger inlet where the cracking reaction will cool the process stream, then pass through at least some of the heat exchanger to be re-heated, and then pass through the catalyst cartridge associated with a process fluid heat exchanger outlet where the cracking reaction will again cool the process stream.
  • the first and second catalyst cartridges may be the same, or may differ from one another.
  • the reactor module may comprise additional catalyst cartridges to contact the process stream, for example third, fourth, or further catalyst cartridges, each associated with a process fluid heat exchanger inlet or with a process fluid heat exchanger outlet.
  • the reactor module may comprise at least one electrically heated catalyst.
  • the electrically heated catalyst may be arranged such that process fluid passing from the process fluid heat exchanger outlet to the process fluid module outlet passes through an electrically heated catalyst.
  • the electrically heated catalyst may be arranged such that process fluid passing from the process fluid module inlet to the process fluid heat exchanger inlet passes through an electrically heated catalyst.
  • the electrically heated catalyst may comprise a catalyst material arranged to contact a process fluid passing therethrough to catalyse a reaction to convert ammonia in the process fluid into hydrogen.
  • the inclusion of an electrically heated catalyst, particularly between the process fluid heat exchanger outlet to the process fluid module outlet, may be particularly beneficial for dealing with non-steady state operation of the reactor module, for example during start-up, or a change in hydrogen demand.
  • the at least one electrically heated catalyst may comprise two, three, or four electrically heated catalysts. Some or all of the electrically heated catalysts may be arranged in series.
  • the electrically heated catalysts may be located upstream of the heat exchanger along the process fluid flow path, downstream of the heat exchanger along the process fluid flow path, or there may be one or more electrically heated catalysts located upstream and downstream of the heat exchanger along the process fluid flow path.
  • the reactor module may comprise a housing within which the heat exchanger and catalyst cartridge are located. This may facilitate transport of the reactor module. If the reactor module comprises additional components they may also be located within the housing.
  • the housing may be formed by walls enclosing a housing volume. The walls and housing volume may and be any suitable shape.
  • the housing may comprise a tubular, for example cylindrical, portion which may be closed by flat or domed endcaps. To simplify manufacture, the walls of the housing may be substantially flat.
  • the housing may define a cuboid having six major walls.
  • the housing may include a housing opening through which access to the internal volume and components of the reactor module therein is possible. The housing opening may be closed by an access panel or door to restrict access to the internal volume.
  • the housing may be thermally insulated. At least some areas of some, or all, of the walls of the housing may include a thermal insulating layer which has a lower thermal conductivity than the material from which the walls are fabricated.
  • the housing volume not occupied by other components may be partially or fully occupied by an insulating material.
  • the insulating material may be provided in the form of sheets or shaped segments to facilitate installation and replacement.
  • the heat exchanger may be any suitable form of heat exchanger. The inventors have found that a welded plate heat exchanger having a plate side and a shell side is particularly suitable for this application. They have found that the geometry of this sort of heat exchanger is particularly suitable as the pressure drops across each side of the heat exchanger can be kept quite low while maintaining acceptable heat transfer from working fluid to process fluid.
  • Some, or all, of the plates of the heat exchanger may be formed by any suitable process, for example stamped from a metal sheet. Some, or all, of the plates of the heat exchanger may comprise corrugations that define channels through the heat exchanger. Within the heat exchanger a plate may define a barrier between a process fluid and a working fluid such that a plurality of alternating flow paths of process fluid and working fluid are defined along the heat exchanger.
  • the heat exchanger may be arranged such that the process fluid passes through the plate side of the heat exchanger.
  • the heat exchanger may comprise an internal plate side inlet manifold adjacent the heat exchanger plate side inlet to distribute the process fluid.
  • the heat exchanger may comprise an internal plate side outlet manifold adjacent the heat exchanger plate side outlet to collect fluid.
  • the inclusion of internal and / or external plate side manifolds may provide a convenient location in which to arrange a catalyst cartridge.
  • a working fluid shell side inlet of the heat exchanger may be arranged closer to process fluid plate side outlet of the heat exchanger than the working fluid shell side outlet to provide a counter-current heat exchanger flow.
  • the internal plate side inlet manifold and I or internal plate side outlet manifold may each comprise a void.
  • the heat exchanger may comprise a plate side void through which process fluid must flow as the process fluid passes between the heat exchanger plate side inlet and the heat exchanger plate side outlet. Any such voids may be any suitable shape.
  • The, or each, void may have a substantially constant cross-sectional size and shape along a void axis, or may taper in one direction along the void axis. Any, or all, of the voids may be substantially cylindrical in shape. Such void shapes may facilitate the insertion or removal of an object into the void.
  • An object may be inserted into a void through an access port.
  • the access port may be the process fluid inlet, the process fluid outlet, or another access port formed in the heat exchanger.
  • the catalyst cartridge may be associated with a process fluid heat exchanger inlet and / or a process fluid heat exchanger outlet by being removably arranged within the internal plate side inlet manifold or the internal plate side outlet manifold.
  • the catalyst cartridge may be movable relative to the heat exchanger, for example by an actuator, such as a linear actuator, piston, motor, lead screw or other drive means.
  • the heat exchanger may comprise a welded plate heat exchanger having a plate side and a shell side and arranged such that the process fluid passes through the plate side of the heat exchanger and the heat exchanger comprises an internal plate side inlet manifold and an internal plate side outlet manifold, and the catalyst cartridge may be associated with a process fluid heat exchanger inlet by being removably arranged within the internal plate side inlet manifold and a second catalyst cartridge may be associated with a process fluid heat exchanger outlet by being removably arranged within the internal plate side outlet manifold.
  • This provides an arrangement in which two catalyst cartridges are arranged in the heat exchanger spaced between the inlet and outlet which provides an initial conversion of at least some ammonia in the process fluid into hydrogen adjacent the inlet of the heat exchanger which reduces the process fluid temperature, then allows the process fluid to be heated by the working fluid as the process fluid passes to the catalyst cartridge in the internal plate side outlet manifold where further ammonia in the process fluid can be converted into hydrogen.
  • the reactor module may include at least one access port closed by a cover. Removal of the cover may allow access to one of the internal plate side inlet manifold and the internal plate side outlet manifold such that a catalyst cartridge located therein can be removed through the access port.
  • the process fluid inlet port and an access port allowing access to the internal plate side outlet manifold may be located adjacent one another in a first end of the reactor module.
  • the process fluid outlet port and an access port allowing access to the internal plate side inlet manifold may be located adjacent one another in a first end of the reactor module.
  • the invention extends to a catalyst cartridge for a comprising a catalyst material arranged to contact a process fluid passing therethrough to catalyse a reaction to convert ammonia in the process fluid into hydrogen, the catalyst cartridge extending along a first axis and having an axial opening and a transverse opening such that a process fluid can flow into or out of the catalyst cartridge along the first axis and can flow out of or into the catalyst cartridge transverse to the first axis.
  • the catalyst cartridge may be suitable for use with an ammonia cracker reactor module as described herein.
  • Providing a catalyst cartridge from which fluid can flow transverse to the first axis, for example perpendicular to the first axis provides a catalyst cartridge that is particularly suitable for arrangement within an internal inlet or outlet plate side manifold of a shell and plate heat exchanger.
  • the catalyst cartridge may extend along a catalyst axis and may comprise an axial flow support which carries the catalyst material.
  • the axial flow support may define a plurality of flow channels which extend substantially parallel with a catalyst cartridge axis. This type of axial flow support is known from the automotive exhaust field and is easily obtainable.
  • the support may be metallic or ceramic.
  • An axial flow support my substantially restrict flow in a non-axial direction.
  • the axial flow support may define a plurality of radial flow gaps.
  • the axial flow support may comprise a plurality of discs separated from one another along the axis to define the radial flow gaps.
  • the axial flow support may be a single component, in which the radial flow gaps are defined by a plurality of radial slots formed in the axial flow support.
  • the dimensions of the radial flow gaps may vary along a length of the catalyst as this may allow the flow resistance though the radial flow gap to be altered along the length of the axial flow support. This may allow the residence time within the axial flow support to be adjusted during design of the catalyst cartridge.
  • the size of the radial flow gaps may be defined by an axial extent of the gap, particularly for an axial flow support comprising a plurality of discs.
  • the size of the radial flow gaps may additionally, or alternatively, be defined by a radial extent of the gap.
  • the catalyst cartridge may comprise a free flow support, for example an open-cell porous support, carrying the catalyst material.
  • a free flow support may allow both radial and axial flow though the support, and into and out of the support.
  • a catalyst cartridge may comprise both an axial flow support and a free flow support.
  • the catalyst cartridge may extend along a cartridge axis.
  • the catalyst cartridge may comprise cartridge walls.
  • Cartridge walls of the catalyst cartridge may define a housing as mentioned above.
  • Cartridge walls of the catalyst cartridge may define an internal flow channel and an annular flow channel surrounding the internal flow channel.
  • a proximal end of the internal flow channel may define an axial opening and a distal end of the internal flow channel being connected to a distal end of the annular flow channel.
  • An exterior wall of the annular flow channel may define a plurality of transverse openings. This allows a catalyst cartridge to be created in which an axial flow support can be arranged within the internal flow channel while the annular flow channel surrounding the internal flow channel provides transverse or radial flow outlets. This arrangement provides a consistent residence time within the axial flow support for process fluid passing through the catalyst cartridge, while simultaneously allowing the reacted process fluid to be evenly radially distributed (transverse to the axial flow direction) into the heat exchanger manifold.
  • the catalyst cartridge may be substantially cylindrical, and the transverse openings may be perpendicular to the catalyst axis.
  • the invention extends to a fuel system comprising a fuel inlet for a fuel containing ammonia, a fuel outlet, an exhaust gas inlet and an exhaust gas outlet, the fuel system further comprising a reactor module as described above, the exhaust inlet being connected to the working fluid module inlet, the exhaust outlet being connected to the working fluid module outlet, the fuel inlet being connected to the process fluid module inlet and the fuel outlet being connected to the process fluid module outlet.
  • the fuel system may be particularly suitable for use to provide fuel to an internal combustion engine, for example an internal combustion engine driving a generator.
  • the internal combustion engine may be intended for fuelling with hydrogen, or a combination of hydrogen and ammonia.
  • the internal combustion engine may produce a stream of hot exhaust fluid that may be used as a working fluid and be passed into the exhaust inlet of the fuel system to pass through the heat exchanger to heat the fuel, which is the process fluid, to enhance the conversion of ammonia in the fuel to hydrogen.
  • the fuel system may comprise a bypass through which at least some of the fuel passing into the system through the fuel inlet can bypass the reactor module to fuel outlet. This bypass allows for a quick adjustment of the relative concentration of ammonia and hydrogen at the fuel outlet.
  • the system may comprise a valve which can be controlled to vary the ratio of fuel passing into the reactor module to fuel passing through the bypass.
  • the system may comprise valves which can be controlled to vary the ratio of fuel passing into the reactor module to fuel passing through the bypass while keeping the flow through the reactor module substantially constant.
  • the fuel system may comprise an evaporator connected between the fuel inlet and process fluid inlet for heating and evaporating fuel passing from the fuel inlet to the process fluid inlet.
  • the evaporator may be heated by any suitable means, for example direct combustion heating, or electrical heating, or may be heated using waste heat from an engine exhaust or waste heat from an engine liquid coolant stream.
  • the evaporator may be connected between the working fluid module outlet and exhaust outlet and arranged to transfer heat from an exhaust stream flowing between the working fluid module outlet and exhaust outlet to fuel passing from the fuel inlet to the process fluid inlet.
  • the system may further comprise an exhaust treatment unit upstream of the exhaust outlet where the exhaust may be discharged to atmosphere.
  • the exhaust treatment unit may be located upstream of the exhaust outlet and downstream of the evaporator, or other heat exchangers in the fuel system that utilise the same waste heat stream (working fluid).
  • the exhaust treatment unit may comprise an electrically heated catalyst and suitable catalyst materials for catalysing a reaction to lower pollutant levels in the exhaust stream (e.g., catalysing a reaction to convert NOx to nitrogen).
  • the exhaust treatment unit may comprise an inlet to allow ammonia from the fuel supply to be added, for example injected through a nozzle, into the exhaust stream to reduce NOx to nitrogen over the catalyst therein.
  • Figure 1 shows a schematic cross section though a first reactor module
  • Figure 2 shows a schematic cross section though a second reactor module with electrically heated catalysts and a housing
  • Figure 3 shows schematic view of a fuel system including a reactor module
  • Figure 4 shows a schematic cross section though a third reactor module with an insulated housing
  • Figure 5 shows a schematic cross section though a fourth reactor module with external catalyst cartridge pipe sections
  • Figure 6 shows a schematic cross section though a fifth reactor module with external catalyst cartridges within pipes
  • Figure 7 shows a schematic cross section though a sixth reactor module with extended external catalyst cartridges
  • Figure 8 shows a schematic cross section though a seventh reactor module in which a process fluid inlet is at the same end of the reactor module as the process fluid outlet;
  • Figure 9 shows a schematic cross section though an eighth reactor module in which there are electrically heated catalysts between the process fluid heat module inlet and the heat exchanger;
  • Figure 10 shows a schematic cross section though a ninth reactor module in which catalyst cartridges can be dynamically moved into or out of the heat exchanger during use;
  • Figure 11 is a schematic cross section though a first catalyst cartridge
  • Figure 12 is a schematic cross section though a second catalyst cartridge
  • Figure 13 is a schematic cross section though a third catalyst cartridge
  • Figure 14 is a schematic cross section though a fourth catalyst cartridge.
  • Figure 15 is a view of a cross section through plates of a welded plate heat exchanger.
  • Figure 1 shows a schematic cross section though an ammonia cracker reactor module 1 comprising a heat exchanger 2, and a catalyst cartridge 4.
  • the reactor module 1 comprises a second catalyst cartridge 4’.
  • the reactor module 1 comprises a process fluid module inlet 6, a process fluid module outlet 8, a working fluid module inlet 10 and a working fluid module outlet 12.
  • the inlets and outlets 6,8,10,12 are defined by a location at which a flow path, such as a pipe, pass through a notional boundary 14 of the reactor module 1 .
  • the heat exchanger 2 and catalyst cartridges 4 are arranged such that a process fluid entering the reactor module 1 through the process fluid module inlet 6 passes through the catalyst cartridge and heat exchanger before passing to the process fluid module outlet 8.
  • the catalyst cartridge 4,4’ each comprise a catalyst material arranged to contact a process fluid passing therethrough to catalyse a reaction to convert ammonia in the process fluid into hydrogen.
  • a process fluid can pass into the reactor module 1 along arrow 20 and out of the reactor module along arrow 22.
  • a working fluid can pass into the reactor module 1 along arrow 24 and out of the reactor module along arrow 26.
  • the heat exchanger 2 is arranged such that a working fluid entering the reactor module 1 through the working fluid module inlet 10 passes through the heat exchanger before passing to the working fluid module outlet 12.
  • the heat exchanger 2 is arranged to transfer heat between a process fluid and a working fluid flowing therethrough.
  • the catalyst cartridges 4, 4’ are removably associated with a process fluid heat exchanger inlet 16 and / or a process fluid heat exchanger outlet 18 such that the catalyst cartridges 4,4’ can be separated from the heat exchanger 2.
  • a process fluid heat exchanger inlet 16 and I or a process fluid heat exchanger outlet 18 there are various ways in which the catalyst cartridges 4,4’ can be removably associated with a process fluid heat exchanger inlet 16 and I or a process fluid heat exchanger outlet 18 and these will be described in more detail in connection with later figures.
  • FIG. 2 shows a reactor module 101.
  • the reactor module 101 comprises many parts that are similar in type and function to those of the reactor 1 of Figure 1 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 101 differs from reactor module 1 in that the reactor module 101 includes a housing 28 at the boundary 114 and the reactor module 101 also comprises electrically heated catalysts 30.
  • the electrically heated catalysts 30 are arranged such that fluid flowing from the process fluid heat exchanger outlet 118 to the process fluid module outlet 108 passes through the electrically heated catalysts 30.
  • FIG 3 shows a fuel system 32 which includes the reactor module 101 of Figure 2.
  • the fuel system 32 in this case is for supplying a fuel to an internal combustion engine 34 which may be part of an electricity generator (not shown).
  • the fuel system 32 also comprises an exhaust gas inlet 42 which, in this example, is connected to an exhaust from the engine 34.
  • the fuel system 32 also comprises an exhaust gas outlet 44 which, in this example, vents exhaust gas from the engine to the atmosphere.
  • the fuel system further comprises the reactor module 101.
  • the exhaust inlet 42 is connected to the working fluid module inlet 110 and the exhaust outlet 44 is connected to the working fluid module outlet 112.
  • the fuel inlet 36 is connected to the process fluid module inlet 106 and the fuel outlet 40 being is connected to the process fluid module outlet 108.
  • the fuel system 32 further comprises an exhaust treatment unit 46 between the working fluid module outlet 112 and the exhaust outlet 44.
  • the exhaust treatment unit 46 is an electrically heated catalyst for treating exhaust gasses from the engine 34.
  • An evaporator 48 is arranged between the fuel inlet 36 and the process fluid module inlet 106. The evaporator 48 heats the fuel prior to the fuel passing into the reactor module 101.
  • the evaporator 48 is arranged between the working fluid module outlet 112 and the exhaust treatment unit 46. This allows the evaporator 48 to use heat remaining in the working (exhaust) fluid after it passes through the reactor module 101.
  • the fuel system 32 also comprises a valve 50 adjacent the fuel inlet 36.
  • the valve 50 controls the flow rate of fuel from the fuel inlet 36 to the evaporator 48 and the flow rate of fuel from the fuel inlet 36 into a bypass 52 through which fuel can pass from the fuel inlet 36 to the fuel outlet 40 without passing through the reaction module 101.
  • the hot exhaust from the engine 34 passes into the exhaust inlet 42 and flows through the heat exchanger 102 to heat the process fluid, in this case the fuel, passing therethrough.
  • the exhaust then passes through the evaporator 48 to heat the fuel before it enters the reactor module 101.
  • the exhaust then passes through the exhaust treatment unit 46 before being released to atmosphere.
  • the controller controls the electrically heated catalysts 30 so that at least some of the fuel passing therethrough is converted to hydrogen and nitrogen and the mixture of hydrogen and ammonia can then be used as a fuel to start the engine 34.
  • the controller 54 also controls the electrically heated catalyst of the exhaust treatment unit 46 to treat the exhaust gas prior to the release of the exhaust into the atmosphere.
  • the controller can switch off the electrically heated catalysts 30 and electrically heated catalyst of the exhaust treatment unit 46.
  • the controller can reactivate one, some, or all of these electrically heated catalysts 30 and electrically heated catalyst of the exhaust treatment unit 46 should the controller receive an indication from the engine 34, or an external input, that such activation is required. This may be required should a quick increase in engine output, or other transient operation, be required.
  • the controller 54 can also control the valve 50 to vary the flow of fuel through the reactor module 101 and the bypass 52 to vary the ratio of hydrogen and ammonia that reaches the fuel outlet 40. This can be varied depending on the required power output from the engine 34.
  • FIG 4 shows schematic cross section though a third reactor module 201.
  • the reactor module 201 comprises many parts that are similar in type and function to those of the reactor 101 of Figure 2 and such components are labelled with similar reference numerals incremented by 100.
  • the housing 128 includes an insulating material 56 therein to reduce the heat loss from the heat exchanger 202.
  • the catalyst cartridge 204 associated with the process fluid heat exchanger inlet 216 is located within a void 58 which forms an inlet manifold 60 for the heat exchanger 202.
  • the catalyst cartridge 204’ associated with the process fluid heat exchanger outlet 218 is located within a void 58’ which forms an outlet manifold 60’ for the heat exchanger 202.
  • the catalyst cartridges 204,204’ are located within the manifolds 60,60’, the catalyst cartridges 204,204’ have outlets that are transverse to an axis along which the catalyst cartridge 204,204’ extends.
  • Access ports 62,62’ are associated with the inlet manifold 60 and the outlet manifold 60’ and are closed by covers 64,64’. Removal of the covers 64,64’ allows access to the voids 58,58’ to allow a user to remove the catalyst cartridges 204,204’ though the access port 62,62’.
  • FIG. 5 shows schematic cross section though a fourth reactor module 301.
  • the reactor module 301 comprises many parts that are similar in type and function to those of the reactor 201 of Figure 4 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 301 comprises catalyst cartridges 304,304’ that are located outside the voids 158,158’ of the heat exchanger 302.
  • the catalyst cartridges 304,304’ comprise a housing 66 which comprise flanged connectors 68 at opposing ends to allow them to be removably coupled into pipework.
  • catalyst supports within the catalyst cartridges can be axial flow supports oriented parallel to the housing, or can be open-cell porous supports.
  • FIG 6 shows schematic cross section though a fifth reactor module 401.
  • the reactor module 401 comprises many parts that are similar in type and function to those of the reactor 301 of Figure 5 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 401 comprises catalyst cartridges 404,404’ that are located outside the voids 258,258’ of the heat exchanger 402.
  • the catalyst cartridges 404,404’ are located within the inlet and outlet pipes 70,72 of the heat exchanger 402.
  • the catalyst cartridges 404,404’ can be inserted into, and removed from, the inlet or outlet pipes 70,72 via the access ports 262,262’, or when the inlet or outlet pipes 70,72 of the heat exchanger 402 is separated from other pipework.
  • FIG 7 shows schematic cross section though a sixth reactor module 501.
  • the reactor module 501 comprises many parts that are similar in type and function to those of the reactor 401 of Figure 6 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 501 comprises catalyst cartridges 504,504’ that are located partially within and partially outside the voids 358,358’ of the heat exchanger 502.
  • catalyst supports within the catalyst cartridges located outside the voids 358,358’ can be axial flow supports oriented parallel to the housing, or can be open-cell porous supports, while the portion of the catalyst cartridges 504,504’ located within the voids 358,358’ comprise transverse outlets.
  • FIG 8 shows schematic cross section though a seventh reactor module 601.
  • the reactor module 601 comprises many parts that are similar in type and function to those of the reactor 501 of Figure 7 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 601 has a process fluid module inlet 606 and a process fluid module outlet 608 at the same end of the housing 528 of the reactor module 601 rather than at an opposite end of the reactor module 601. This can provide a greater degree of flexibility in placing the reactor module 601 and may provide advantages in compensating for thermal expansion in a system incorporating the reactor module 601 . It should be understood that the process fluid module inlet and outlet 606,608, and the working fluid module inlet and outlet 610,612 can be arranged anywhere on the housing 528.
  • FIG 9 shows schematic cross section though a seventh reactor module 701.
  • the reactor module 701 comprises many parts that are similar in type and function to those of the reactor 601 of Figure 8 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 701 comprises electrically heated catalysts 630’ between the process fluid module inlet 706 and heat exchanger 702.
  • FIG 10 shows schematic cross section though an eighth reactor module 801.
  • the reactor module 801 comprises many parts that are similar in type and function to those of the reactor 701 of Figure 9 and such components are labelled with similar reference numerals incremented by 100.
  • the reactor module 801 comprises catalyst cartridges 804,804’ which can be moved into or out of the heat exchanger 802 by linear actuators 1000.
  • the actuators 1000 act on the catalyst cartridges 804,804’ via rods 1002.
  • the rods 1002 pass through a guide tube 1006 which is sealed by a sliding seal 1004.
  • the catalyst cartridge 804 can be moved to, or away from, the process fluid heat exchanger inlet 816 and catalyst cartridge 804’ can be moved to, or away from, the process fluid heat exchanger outlet 818.
  • Moving the catalyst cartridges 804,804’ away from the associated process fluid heat exchanger inlet or outlet 816,818 provides a route via which process fluid passing through the heat exchanger 802 can bypass one or both catalyst cartridges 804,804’ and this therefore provides a way to dynamically alter the extent of conversion of ammonia in the process fluid to hydrogen.
  • These movements may be in response to a downstream application demand, for example increased or decreased fuel demand by an internal combustion engine.
  • the linear actuators 1000 can be controlled by a controller which may also control the electrically heated catalysts 730, or other components of a wider system to which the reactor module 801 may be attached.
  • FIG 11 shows a schematic cross section though a first catalyst cartridge 74.
  • the catalyst cartridge 74 comprises an axial flow support 76 onto which a catalyst material 78 is coated.
  • the axial flow support 76 is substantially cylindrical in shape, but has a plurality of annular slots 80 therein to provide transverse outlets 82.
  • the transverse outlets 82 provide a route for gas that enters an axial end 84 of the axial flow support 76 to pass through the axial flow support 76 and enter the inlets 86 to the process side of the heat exchanger.
  • FIG 12 is a schematic cross section though a second catalyst cartridge 174.
  • the catalyst cartridge 174 comprises an open-cell porous flow support 176 onto which a catalyst material 178 is coated.
  • the open-cell porous flow support 176 is substantially cylindrical in shape and allows axial and radial flow to allow gas that enters an axial end 184 of the open-cell porous flow support 176 to pass through the axial flow support 176 an enter the inlets 186 to the process side of the heat exchanger.
  • FIG 13 is a schematic cross section though a third catalyst cartridge 274.
  • the catalyst cartridge 274 comprises an axial flow support 276 onto which a catalyst material 278 is coated.
  • the axial flow support 276 is substantially cylindrical in shape and is contained in an inner housing 88 defining an internal flow channel.
  • Surrounding the inner housing 88 is an annular flow channel 90 defined by an exterior wall 92, in this case providing a cartridge housing, which includes perforations or slots defining a plurality of transverse outlets 82 through which a fluid in the annular flow channel 90 can pass to the enter the inlets 286 to the process side of the heat exchanger.
  • a cartridge housing could be provided for cartridges that do not include radial outlets.
  • the catalyst cartridge 274 includes an axial opening 94 through which a process fluid can enter an axial end 284, in this case a proximal end, of the axial flow support 276 and pass along the axial flow support 278 until it leaves a distal end of the axial flow support 276.
  • the distal end of the axial flow support 276 is connected to the annular flow channel 90.
  • An annular seal 96 prevents fluid from bypassing the catalyst cartridge 274. Such a seal can be used with any other catalyst cartridge.
  • FIG 14 is a schematic cross section though a fourth catalyst cartridge 374.
  • the catalyst cartridge 374 is similar to the catalyst cartridge 274 and like parts will be given the same reference numerals incremented by 100.
  • the catalyst cartridge 374 differs from catalyst cartridge 274 in that the axial flow support 376 is longer and the catalyst cartridge is intended to be installed partly within and partly outside a void of a heat exchanger. For this reason the outer wall 192 does not include transverse outlets 82 along its full length.
  • Figure 15 is a view of a cross section through some of the plates 98 of a welded plate heat exchanger 100.
  • the plates 98 are made of a metal which is pressed to form a plurality of corrugations which define flow channels.
  • the plates 98 are welded together to define a plate side channels and shell side channels of a heat exchanger.
  • This cross section also shows part of a cylindrical void 58 into which a catalyst cartridge could be inserted.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

L'invention concerne un module de réacteur de craquage d'ammoniac comprenant un échangeur de chaleur, et une cartouche de catalyseur. Le module de réacteur comprend une entrée de module de fluide de traitement, une sortie de module de fluide de traitement, une entrée de module de fluide de travail et une sortie de module de fluide de travail. L'échangeur de chaleur et la cartouche de catalyseur sont agencés de telle sorte qu'un fluide de traitement entrant dans le module de réacteur par l'entrée de module de fluide de traitement passe à travers la cartouche de catalyseur et l'échangeur de chaleur avant de passer à la sortie de module de fluide de traitement. La cartouche de catalyseur comprend un matériau catalyseur agencé pour entrer en contact avec un fluide de traitement passant à travers celui-ci pour catalyser une réaction pour convertir l'ammoniac dans le fluide de traitement en hydrogène. L'échangeur de chaleur est agencé de telle sorte qu'un fluide de travail entrant dans le module de réacteur à travers l'entrée de module de fluide de travail passe à travers l'échangeur de chaleur avant de passer à la sortie de module de fluide de travail, l'échangeur de chaleur étant agencé pour transférer de la chaleur entre un fluide de traitement et un fluide de travail s'écoulant à travers celui-ci. La cartouche de catalyseur est associée de manière amovible à une entrée d'échangeur de chaleur de fluide de traitement et/ou à une sortie d'échangeur de chaleur de fluide de traitement de telle sorte que la cartouche de catalyseur peut être séparée de l'échangeur de chaleur. L'invention s'étend à une cartouche de catalyseur pour un tel module de réacteur et à un système de carburant utilisant un tel module.
PCT/GB2024/051627 2023-06-30 2024-06-26 Module de réacteur Pending WO2025003654A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2310076.1A GB2631481A (en) 2023-06-30 2023-06-30 Reactor module
GB2310076.1 2023-06-30

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WO2025003654A1 true WO2025003654A1 (fr) 2025-01-02

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Publication number Priority date Publication date Assignee Title
CN119746724B (zh) * 2024-12-27 2025-11-25 佛山绿动氢能科技有限公司 氨裂解制氢装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB363300A (en) * 1930-08-01 1931-12-17 Dupont Ammonia Corp Improved method of and apparatus for decomposing ammonia
EP2105601B1 (fr) * 2008-03-28 2010-09-01 Hitachi Ltd. Système motorisé
CN208532222U (zh) * 2018-08-02 2019-02-22 扬州伟达机械有限公司 一种ax氨气分解发生装置
WO2024050149A1 (fr) * 2022-08-06 2024-03-07 Wall James L Ii Systèmes et méthodes de production d'hydrogène à partir d'ammoniac à l'aide d'unités de catalyseur doubles en série

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5976723A (en) * 1997-03-12 1999-11-02 Boffito; Claudio Getter materials for cracking ammonia
CN111137856B (zh) * 2020-03-03 2024-06-04 大连海事大学 一种撬装式移动现场制氢一体机
CN114524409A (zh) * 2022-03-22 2022-05-24 芜湖朗卓新材料科技有限公司 一种节能型大气量氨分解制氢装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB363300A (en) * 1930-08-01 1931-12-17 Dupont Ammonia Corp Improved method of and apparatus for decomposing ammonia
EP2105601B1 (fr) * 2008-03-28 2010-09-01 Hitachi Ltd. Système motorisé
CN208532222U (zh) * 2018-08-02 2019-02-22 扬州伟达机械有限公司 一种ax氨气分解发生装置
WO2024050149A1 (fr) * 2022-08-06 2024-03-07 Wall James L Ii Systèmes et méthodes de production d'hydrogène à partir d'ammoniac à l'aide d'unités de catalyseur doubles en série

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